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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124958, 2025 Jan 05.
Article in English | MEDLINE | ID: mdl-39146627

ABSTRACT

Vanillin is a commonly used synthetic flavoring agent in daily life. However, excessive intake of vanillin may pose risks to human health. Therefore, there is an urgent need for rapid and sensitive detection methods for vanillin. In this study, we developed a fluorescent sensor based on Cd-MOF for the sensitive and selective recognition of vanillin. The presence of vanillin leads to significant fluorescence quenching of Cd-MOF due to competitive absorption and photoinduced electron transfer (PET). The limit of detection was determined to be 39.6 nM, which is the lowest-among the reported fluorescent probes. The sensor was successfully applied for the detection of vanillin in real samples such as powdered milk and milk, with a recovery rate ranging from 96.88 % to 104.83 %. Furthermore, by immobilizing the Cd-MOF probe into a polyvinyl alcohol (PVA) film, we achieved a portable and visual detection composite materials for vanillin.


Subject(s)
Benzaldehydes , Metal-Organic Frameworks , Milk , Spectrometry, Fluorescence , Benzaldehydes/analysis , Benzaldehydes/chemistry , Milk/chemistry , Animals , Spectrometry, Fluorescence/methods , Metal-Organic Frameworks/chemistry , Powders , Fluorescent Dyes/chemistry , Limit of Detection , Cadmium/analysis
2.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124989, 2025 Jan 05.
Article in English | MEDLINE | ID: mdl-39154403

ABSTRACT

A newly developed 2H5MA-MOF sensor by covalently linking NH2-MIL-53(Al) with 2'-Hydroxy-5'-methylacetophenon, designed for highly sensitive and selective detection of Cd2+ ions using fluorometric methods. Detailed structural and morphological analyses confirmed the sensor's unique properties. It demonstrated an impressive linear detection range from 0 to 2 ppm, with an exceptionally low detection limit of 5.77 × 10-2 ppm and a quantification limit of 1.75 × 10-1 ppm, indicating its high sensitivity (R2 = 0.9996). The sensor also responded quickly, detecting Cd2+ within just 30 s at pH 4. We successfully tested it on real samples of tap water and human blood plasma, achieving recovery rates between 96 % and 104 %. The accuracy of these findings was further validated by comparison with ICP-OES. Overall, the 2H5MA-MOF sensor shows great potential for fast, ultra-sensitive, and reliable detection of Cd2+ ions, making it a promising tool for environmental and biomedical applications.


Subject(s)
Cadmium , Drinking Water , Limit of Detection , Metal-Organic Frameworks , Cadmium/blood , Cadmium/analysis , Humans , Metal-Organic Frameworks/chemistry , Drinking Water/analysis , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/blood , Ions/blood , Hydrogen-Ion Concentration
3.
J Environ Sci (China) ; 148: 174-187, 2025 Feb.
Article in English | MEDLINE | ID: mdl-39095155

ABSTRACT

Cost-effective CO2 adsorbents are gaining increasing attention as viable solutions for mitigating climate change. In this study, composites were synthesized by electrochemically combining the post-gasification residue of Macadamia nut shell with copper benzene-1,3,5-tricarboxylate (CuBTC). Among the different composites synthesized, the ratio of 1:1 between biochar and CuBTC (B 1:1) demonstrated the highest CO2 adsorption capacity. Under controlled laboratory conditions (0°C, 1 bar, without the influence of ambient moisture or CO2 diffusion limitations), B 1:1 achieved a CO2 adsorption capacity of 9.8 mmol/g, while under industrial-like conditions (25°C, 1 bar, taking into account the impact of ambient moisture and CO2 diffusion limitations within a bed of adsorbent), it reached 6.2 mmol/g. These values surpassed those reported for various advanced CO2 adsorbents investigated in previous studies. The superior performance of the B 1:1 composite can be attributed to the optimization of the number of active sites, porosity, and the preservation of the full physical and chemical surface properties of both parent materials. Furthermore, the composite exhibited a notable CO2/N2 selectivity and improved stability under moisture conditions. These favorable characteristics make B 1:1 a promising candidate for industrial applications.


Subject(s)
Carbon Dioxide , Metal-Organic Frameworks , Carbon Dioxide/chemistry , Adsorption , Metal-Organic Frameworks/chemistry , Air Pollutants/chemistry , Charcoal/chemistry
4.
J Environ Sci (China) ; 149: 374-385, 2025 Mar.
Article in English | MEDLINE | ID: mdl-39181650

ABSTRACT

Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.


Subject(s)
Ammonia , Copper , Iron , Metal-Organic Frameworks , Nitrates , Water Pollutants, Chemical , Ammonia/chemistry , Copper/chemistry , Nitrates/chemistry , Metal-Organic Frameworks/chemistry , Iron/chemistry , Water Pollutants, Chemical/chemistry , Catalysis , Models, Chemical , Oxidation-Reduction , Kinetics
5.
Food Chem ; 462: 140666, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39208728

ABSTRACT

To improve the adsorption affinity and selectivity of fipronils (FPNs), including fipronil, its metabolites and analogs, a magnetic covalent organic framework (Fe3O4@COF-F) with copious fluorine affinity sites was innovatively designed as an adsorbent of magnetic solid-phase extraction (MSPE). The enhanced surface area, pore size, crystallinity of Fe3O4@COF-F and its exponential adsorption capacities (187.3-231.5 mg g-1) towards fipronils were investigated. Combining MSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), an analytical method was established for the selective determination of fipronils in milk and milk powder samples. This method achieved high sensitivity (LODs: 0.004-0.075 ng g-1), satisfactory repeatability and accuracy with spiked recoveries ranging from 89.9% to 100.3% (RSDs≤5.1%). Overall, the constructed Fe3O4@COF-F displayed great potential for the selective enrichment of fipronils, which could be ascribed to fluorine­fluorine interaction. This method proposed a feasible and promising strategy for the development of functionalized COF and broadened its application in fluorine containing hazards detection.


Subject(s)
Fluorine , Food Contamination , Metal-Organic Frameworks , Milk , Pyrazoles , Solid Phase Extraction , Tandem Mass Spectrometry , Pyrazoles/chemistry , Food Contamination/analysis , Fluorine/chemistry , Milk/chemistry , Animals , Metal-Organic Frameworks/chemistry , Adsorption , Chromatography, High Pressure Liquid , Insecticides/chemistry , Insecticides/analysis , Limit of Detection
6.
Food Chem ; 462: 141027, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39213963

ABSTRACT

Integrating multiple functionalities into a single entity is highly important, especially when a broad spectrum of application is required. In the present work, we synthesized a novel manganese-based MOF (denoted as UoZ-6) that functions as a cold/hot-adapted and recyclable oxidase nanozyme (Km 0.085 mM) further developed for ratiometric-based colorimetric and color tonality visual-mode detection of nitrite in water and food. Nitrite ions promote the diazotization process of the oxTMB product, resulting in a decay in the absorbance signal at 652 nm and the emergence of a new signal at 461 nm. The dual-absorbance ratiometric platform for nitrite ion detection functions effectively across a wide temperature range (0 °C to 100 °C), offering a linear detection range of 5-45 µM with a detection limit of 0.15 µM using visual-mode. This approach is sensitive, reliable, and selective, making it effective for detecting nitrite ions in processed meat and water.


Subject(s)
Colorimetry , Nitrites , Nitrites/analysis , Colorimetry/methods , Metal-Organic Frameworks/chemistry , Oxidoreductases/chemistry , Oxidoreductases/metabolism , Limit of Detection , Cold Temperature , Hot Temperature , Food Contamination/analysis , Color
7.
Food Chem ; 462: 140922, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39213967

ABSTRACT

Rapid screening for foodborne pathogens is crucial for food safety. A rapid and one-step electrochemical sensor has been developed for the detection of Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Salmonella typhimurium (S. typhimurium). Through the construction of aptamer/two-dimensional carboxylated Ti3C2Tx (2D C-Ti3C2Tx)/two-dimensional Zn-MOF (2D Zn-MOF) composites, the recognition elements, signal tags, and signal amplifiers are integrated on the electrode surface. Pathogens are selectively captured using the aptamer, which increases the impedance of the electrode surface,leads to a decrease in the 2D Zn-MOF current. Bacteria can be rapidly quantified using a one-step detection method and the replacement of aptamers. The detection limits for E. coli, S. aureus, and S. typhimurium are 6, 5, and 5 CFU·mL-1, respectively. The sensor demonstrated reliable detection capabilities in real-sample testing. Therefore, the one-step sensor based on the 2D Zn-MOF and 2D C-Ti3C2Tx has significant application value in the detection of foodborne pathogens.


Subject(s)
Electrochemical Techniques , Escherichia coli , Salmonella typhimurium , Staphylococcus aureus , Zinc , Staphylococcus aureus/isolation & purification , Salmonella typhimurium/isolation & purification , Zinc/analysis , Escherichia coli/isolation & purification , Electrochemical Techniques/instrumentation , Biosensing Techniques/instrumentation , Metal-Organic Frameworks/chemistry , Food Microbiology , Titanium/chemistry , Limit of Detection , Electrodes , Food Contamination/analysis
8.
Food Chem ; 462: 141007, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39216376

ABSTRACT

In this study, covalent organic frameworks (COFs) were grown in situ on magnetic nitrogen-doped graphene foam (MNGF), and the resulting composite of COFs-modified MNGF (MNC) was wrapped by molecularly imprinted polymers (MNC@MIPs) for specifically capturing SAs. A magnetic solid phase extraction (MSPE) method for SAs was established using MNC@MIPs with good magnetic responsiveness. The adsorption performance of MNC@MIPs was superior to that of non-molecularly imprinted polymers (MNC@NIPs), with shorter adsorption/desorption time and higher imprinting factors. A high-efficiency SAs analytical method was developed by fusing HPLC and MNC@MIPs-based MSPE. This approach provides excellent precision, a low detection limit, and wide linearity. By analyzing fish samples, the feasibility of the approach was confirmed, with SAs recoveries and relative standard deviations in spiked samples in the ranges of 77.2-112.7 % and 2.0-7.2 %, respectively. This study demonstrated the potential use of MNC@MIPs-based MSPE for efficient extraction and quantitation of trace hazards in food.


Subject(s)
Fishes , Food Contamination , Metal-Organic Frameworks , Molecularly Imprinted Polymers , Solid Phase Extraction , Sulfonamides , Solid Phase Extraction/methods , Solid Phase Extraction/instrumentation , Animals , Molecularly Imprinted Polymers/chemistry , Adsorption , Food Contamination/analysis , Metal-Organic Frameworks/chemistry , Sulfonamides/isolation & purification , Sulfonamides/chemistry , Sulfonamides/analysis , Molecular Imprinting , Polymers/chemistry
9.
Food Chem ; 462: 141063, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39226640

ABSTRACT

In this research, the TT-COF(Fe)@NH2-CNTs was innovatively prepared through a post-modification synthetic process functionalized TT-COF@NH2-CNTs with active site (Fe), where TT-COF@NH2-CNTs was prepared via a one-pot strategy using 5,10,15,20-tetrakis (para-aminophenyl) porphyrin (TTAP), 2,3,6,7-tetra (4-formylphenyl) tetrathiafulvalene (TTF) and aminated carbon nanotubes (NH2-CNTs) as raw materials. The complex TT-COF(Fe)@NH2-CNTs material possessed porous structures, outstanding conductivity and rich catalytic sites. Thus, it can be adopted to construct electrochemical sensor with glassy carbon electrode (GCE). The TT-COF(Fe)@NH2-CNTs/GCE can selectively detect luteolin (Lu) with a wide linear plot ranging from 0.005 to 3 µM and a low limit of detection (LOD) of 1.45 nM (S/N = 3). The Lu residues in carrot samples were determined using TT-COF(Fe)@NH2-CNTs sensor and UV-visible (UV-Vis) approach. This TT-COF(Fe)@NH2-CNTs/GCE sensor paves the way for the quantification of Lu through a cost-efficient and sensitive electrochemical approach, which can make a significant step in the sensing field based on crystalline COFs.


Subject(s)
Electrochemical Techniques , Luteolin , Nanotubes, Carbon , Nanotubes, Carbon/chemistry , Luteolin/chemistry , Luteolin/analysis , Electrochemical Techniques/instrumentation , Limit of Detection , Metal-Organic Frameworks/chemistry , Food Contamination/analysis , Catalytic Domain
10.
Food Chem ; 462: 140936, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39232273

ABSTRACT

Aromatic amino acid oxidation products (AAAOPs) are newly discovered risk substances of thermal processes. Due to its significant polarity and trace level in food matrices, there are no efficient pre-treatment methods available to enrich AAAOPs. Herein, we proposed a magnetic cationic covalent organic framework (Fe3O4@EB-iCOF) as an adsorbent for dispersive magnetic solid-phase extraction (DMSPE). Benefiting from the unique charged characteristics of Fe3O4@EB-iCOF, AAAOPs can be enriched through electrostatic interaction and π-π interactions. Under the optimal DMSPE conditions, the combined HPLC-MS/MS method demonstrated good linearity (R2 ≥ 0.990) and a low detection limit (0.11-7.5 µg·kg-1) for AAAOPs. In addition, the method was applied to real sample and obtained satisfactory recoveries (86.8 % âˆ¼ 109.9 %). Especially, we applied this method to the detection of AAAOPs in meat samples and conducted a preliminarily study on its formation rules, which provides a reliable basis for assessing potential dietary risks.


Subject(s)
Amino Acids, Aromatic , Oxidation-Reduction , Solid Phase Extraction , Solid Phase Extraction/methods , Amino Acids, Aromatic/chemistry , Amino Acids, Aromatic/analysis , Amino Acids, Aromatic/isolation & purification , Tandem Mass Spectrometry , Metal-Organic Frameworks/chemistry , Hot Temperature , Food Contamination/analysis , Chromatography, High Pressure Liquid , Animals , Adsorption , Meat/analysis , Food, Processed
11.
Biomaterials ; 312: 122755, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39151270

ABSTRACT

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.


Subject(s)
Biomimetic Materials , Copper , Humans , Copper/chemistry , Biomimetic Materials/chemistry , Catalysis , Metal-Organic Frameworks/chemistry , Neoplasms/drug therapy , Neoplasms/therapy , Cerium/chemistry , Cell Line, Tumor , Animals , Click Chemistry/methods , Biomimetics/methods , Mice
12.
Chem Commun (Camb) ; 60(76): 10580-10583, 2024 Sep 20.
Article in English | MEDLINE | ID: mdl-39233666

ABSTRACT

Separation of racemic drugs is of great importance and interest in chemistry and pharmacology. Here, we report the bottom-up synthesis of the binaphthyl-based chiral covalent organic frameworks (CCOFs), (R)-BHTP-COF. Then, high-performance liquid chromatography (HPLC) columns were prepared using (R)-BHTP-COF as a chiral stationary phase (CSP). Racemic ibuprofen was successfully baseline-separated on (R)-BHTP-COF-based CSP, and achieved excellent selectivity (α = 2.32) and chromatographic resolution (Rs = 3.39) factors. Meanwhile, the separation of six racemic drugs by the (R)-BHTP-COF-packed column exhibited high resolution, selectivity, and durability. The successful applications indicate the great potential of CCOFs as a novel stationary phase for efficient HPLC separation.


Subject(s)
Ibuprofen , Metal-Organic Frameworks , Naphthalenes , Naphthalenes/chemistry , Naphthalenes/isolation & purification , Chromatography, High Pressure Liquid , Stereoisomerism , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Ibuprofen/chemistry , Ibuprofen/isolation & purification , Molecular Structure , Pharmaceutical Preparations/chemistry , Pharmaceutical Preparations/isolation & purification
13.
Nano Lett ; 24(37): 11520-11528, 2024 Sep 18.
Article in English | MEDLINE | ID: mdl-39234992

ABSTRACT

Small-molecule biomarkers are ubiquitous in biological fluids with pathological implications, but major challenges persist in their quantitative analysis directly in complex clinical samples. Herein, a molecular-sieving label-free surface-enhanced Raman spectroscopy (SERS) biosensor is reported for selective quantitative analysis of trace small-molecule trimetazidine (TMZ) in clinical samples. Our biosensor is fabricated by decorating a superhydrophobic monolayer of microporous metal-organic frameworks (MOF) shell-coated Au nanostar nanoparticles on a silicon substrate. The design strategy principally combines the hydrophobic surface-enabled physical confinement and preconcentration, MOF-assisted molecular enrichment and sieving of small molecules, and sensitive SERS detection. Our biosensor utilizes such a "molecular confinement-and-sieving" strategy to achieve a five orders-of-magnitude dynamic detection range and a limit of detection of ≈0.5 nM for TMZ detection in either urine or whole blood. We further demonstrate the applicability of our biosensing platform for longitudinal label-free SERS detection of the TMZ level directly in clinical samples in a mouse model.


Subject(s)
Biosensing Techniques , Gold , Metal Nanoparticles , Metal-Organic Frameworks , Spectrum Analysis, Raman , Spectrum Analysis, Raman/methods , Animals , Mice , Gold/chemistry , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Humans , Metal-Organic Frameworks/chemistry , Biomarkers/urine , Biomarkers/analysis , Surface Properties , Limit of Detection
14.
BMC Biotechnol ; 24(1): 61, 2024 Sep 15.
Article in English | MEDLINE | ID: mdl-39278901

ABSTRACT

Nanoporous aluminum metal-organic framework (Al-MOF) was synthesized via solvothermal methods and employed as a carrier matrix for in vitro drug delivery of Umbelliferon (Um). The encapsulated Um was gradually released over seven days at 37 °C, using simulated body fluid phosphate-buffered saline (PBS) at pH 7.4 as the release medium. The drug release profile suggests the potential of Al-MOF nanoparticles as effective drug delivery carriers. Structural and chemical analyses of Um-loaded Al-MOF nanoparticles (Um-Al MOF) were conducted using Fourier-transform infrared (FTIR) spectroscopy, X-ray diffractometry (XRD), and ultraviolet-visible (UV-Vis) spectroscopy. Thermal gravimetric analysis (TGA) was employed to investigate the thermal stability of the Al-MOF nanoparticles, while Transmission Electron Microscopy (TEM) was utilized to assess their morphological features. Um-Al MOF nanoparticles demonstrated notable antioxidant and anti-inflammatory properties compared to Um and Al-MOF nanoparticles individually. Moreover, they exhibited significant enhancement in wound healing in an earthworm model. These findings underscore the potential of Al-MOF nanoparticles as a promising drug delivery system, necessitating further investigations to explore their clinical applicability.


Subject(s)
Aluminum , Anti-Inflammatory Agents , Antioxidants , Metal-Organic Frameworks , Oligochaeta , Umbelliferones , Wound Healing , Animals , Antioxidants/chemistry , Antioxidants/pharmacology , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Umbelliferones/chemistry , Umbelliferones/pharmacology , Oligochaeta/drug effects , Wound Healing/drug effects , Anti-Inflammatory Agents/chemistry , Anti-Inflammatory Agents/pharmacology , Aluminum/chemistry , Nanoparticles/chemistry , Drug Liberation , Drug Carriers/chemistry
15.
Talanta ; 280: 126785, 2024 Dec 01.
Article in English | MEDLINE | ID: mdl-39217709

ABSTRACT

In the present research, Fe-based metal-organic frameworks (MIL-101(Fe)-NH2) nanoparticles were synthesized by simple solvothermal methods and used to assay Cr(Ⅵ). The MIL-101(Fe)-NH2 performs dual functions: the 2-aminoterephthalic acid (NH2-BDC) ligand endows a strong fluorescence emission, and the Fe metal nodes are able to facilitate the oxidation of 3,3',5,5'- tetramethylbenzidine (TMB) directly, resulting in the generation of oxidized-TMB (ox-TMB). Our research results showed that reducing agents such as ascorbic acid (AA) can collapse the structures of MIL-101(Fe)-NH2 because of the reduction of Fe3+ by AA, resulting in release of NH2-BDC. In the presence of Cr(Ⅵ), the fluorescence intensity of the MIL-101(Fe)-NH2 + AA system will be decreased due to the competitive reduction of Fe3+ and Cr(Ⅵ). Nevertheless, Cr(Ⅵ) can significantly accelerate the oxidation of TMB by MIL-101(Fe)-NH2 as it boosts the electron transfer rate between Fe3+ and Fe2+. Therefore, a fluorescent/colorimetric dual-mode platform was developed for the detection of Cr(Ⅵ) with an extensive linear range (7.5-750 µg/L and 13.3-1000 µg/L) as well as a remarkably low detection limit (0.99 µg/L and 1.98 µg/L). This MOF with the ability to release ligands not only provides inspiration for the design of new luminescent materials, but also offers a novel and reliable solution for the detection of Cr(Ⅵ).


Subject(s)
Chromium , Colorimetry , Fluorescent Dyes , Metal-Organic Frameworks , Chromium/analysis , Chromium/chemistry , Metal-Organic Frameworks/chemistry , Fluorescent Dyes/chemistry , Colorimetry/methods , Limit of Detection , Benzidines/chemistry , Oxidation-Reduction , Iron/chemistry , Spectrometry, Fluorescence/methods , Peroxidase/chemistry , Peroxidase/metabolism , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry
16.
Anal Chem ; 96(37): 15042-15049, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39219053

ABSTRACT

Despite many luminescent advantages including outstanding absorption coefficient and high quantum yield, pyrene and its derivatives have been suffering from a dramatic aggregation-caused quenching (ACQ) effect. Although the dramatic ACQ effect of pyrene-based fluorophores has been restrained in pyrene-doped metal-organic frameworks (MOFs), the low loading of fluorescent (FL) units substantially impedes the improved luminescent behaviors. Herein, pyrene-based MOFs hydrogel was synthesized with a high loading of pyrene as the unique organic linker blocks instead of a dopant in MOFs. The gel matrix contributed to rigidifying the location of the FL emitters and achieving intensive FL emission and high luminescent stability and therefore efficiently overcoming the ACQ effect. Furthermore, the protonation of pyrene in the MOFs hydrogel remarkably decreased the luminescent intensity, which endowed the FL hydrogel with highly pH-responsive activity in the broad range (pH 4-10). Interestingly, glucose oxidase was immobilized into ZIF-8 as a highly efficient luminescent quencher, which contributed to catalyzing the form of gluconic acid and thus drastically quenching the FL signal of the MOFs hydrogel. Furthermore, the emitter-quencher pair of pyrene-based MOFs hydrogel and glucose oxidase was successfully employed to develop an ultrasensitive FL immunoassay platform for cardiac troponin I (as a model analyte). The limit of detection for cardiac troponin I was 5.2 pg/mL (3σ). The proof-of-principle study demonstrated the thrilling auxiliary effect of tailorable MOFs hydrogel on boosting the feasibility of aqueous insoluble FL chromophores for trace analysis.


Subject(s)
Hydrogels , Metal-Organic Frameworks , Pyrenes , Troponin I , Pyrenes/chemistry , Metal-Organic Frameworks/chemistry , Troponin I/analysis , Troponin I/blood , Hydrogen-Ion Concentration , Humans , Hydrogels/chemistry , Immunoassay/methods , Fluorescent Dyes/chemistry , Fluorescence
17.
Anal Chem ; 96(37): 14926-14934, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39219294

ABSTRACT

In conventional metal-organic framework (MOF) luminophore-involved electrochemiluminescence (ECL) systems, the aggregation-caused quenching commonly exists for the organic luminescent ligands, limiting the ECL efficiency and detection sensitivity. Herein, by employing the aggregation-induced emission luminogen (AIEgen) 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene (H4TCBPE) as a ligand, one high-efficiency ECL emitter (Zr-MOF) was synthesized through a simple hydrothermal reaction. Compared with H4TCBPE monomers and their aggregates, the resultant Zr-MOF possesses the strongest ECL emission, which is mainly attributed to the framework-induced ECL enhancement. Specifically, the heterostructure was prepared by the deposition of silver nanoparticles on TiO2 microflowers and utilized as an efficient coreaction accelerator. Remarkably, the formative heterojunction can increase the interfacial charge transfer efficiency and promote the carrier separation, facilitating the oxidation of coreactant tripropylamine. In this way, a novel aptamer-mediated ECL sensing platform is constructed, achieving the sensitive analysis of adenosine triphosphate with a low detection limit of 0.17 nM. As a proof-of-concept study, this work may enlighten the rational design of new-type MOF-based ECL materials and expand the application scope of the ECL technology.


Subject(s)
Biosensing Techniques , Electrochemical Techniques , Luminescent Measurements , Metal Nanoparticles , Metal-Organic Frameworks , Silver , Titanium , Titanium/chemistry , Silver/chemistry , Metal-Organic Frameworks/chemistry , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Limit of Detection , Adenosine Triphosphate/analysis , Aptamers, Nucleotide/chemistry , Zirconium/chemistry
18.
Environ Sci Technol ; 58(37): 16465-16474, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39219302

ABSTRACT

Metal-organic frameworks (MOFs) represent a distinctive class of nanoporous materials with considerable potential across a wide range of applications. Recently, a handful of MOFs has been explored for the storage of environmentally hazardous fluorinated gases (Keasler et al. Science 2023, 381, 1455), yet the potential of over 100,000 MOFs for this specific application has not been thoroughly investigated, particularly due to the absence of an established force field. In this study, we develop an accurate force field for nonaversive hydrofluorocarbon vinylidene fluoride (VDF) and conduct high-throughput computational screening to identify top-performing MOFs with high VDF adsorption capacities. Quantitative structure-property relationships are analyzed via machine learning models on the combinations of geometric, chemical, and topological features, followed by feature importance analysis to probe the effects of these features on VDF adsorption. Finally, from detailed structural analysis via radial distribution functions and spatial densities, we elucidate the significance of different interaction modes between VDF and metal nodes in top-performing MOFs. By synergizing force-field development, computational screening, and machine learning, our findings provide microscopic insights into VDF adsorption in MOFs that will advance the development of new nanoporous materials for high-performance VDF storage or capture.


Subject(s)
Machine Learning , Metal-Organic Frameworks , Metal-Organic Frameworks/chemistry , Adsorption
19.
Langmuir ; 40(37): 19775-19786, 2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39226467

ABSTRACT

Carbonic anhydrase (CA) plays a crucial role in the CO2 capture processes by catalyzing the hydration of CO2. In this study, we synthesized a bioinspired carbonic anhydrase Zn-MOF (metal-organic framework) incorporating 2-aminoimidazole and Zn2+ as initial constituents. The synthesized Zn-MOF exhibited promising potential for efficiently catalyzing the CO2 hydration. Structural analyses such as SEM, XRD, and BET confirmed that the Zn-MOF crystal consisted of stacked grains with an average size of approximately 36 nm, forming a micron-sized spherical structure. Functionally, Zn-MOF exhibited effective catalytic activity toward both CO2 hydration and ester hydrolysis. The introduction of amino groups significantly enhanced the esterase activity of Zn-MOF to 0.28 U/mg at ambient temperature, which was twice that of ZIF-8. Furthermore, the introduction of amino groups resulted in remarkable hydrothermal stability, with the esterase activity reaching 0.72 U/mg after undergoing hydrothermal treatment at 80 °C for 12 h. Additionally, Zn-MOF exhibited enhanced capability in CO2 hydration at a pH value exceeding 8.5. After six repeated uses, ZIF-8 and Zn-MOF retained approximately 68 and 65% of their initial enzyme activity, respectively, underscoring the potential practical applicability of Zn-MOF in industrial CO2 capture processes. This work showcases the development of a novel Zn-MOF crystal as an efficient CA mimic, effectively emulating the active sites of natural CA using 2-aminoimidazole as a coordinating ligand for Zn2+ coordination. These findings not only advance the field of innovative enzyme mimics but also pave the way for further exploration of industrial CO2 capture catalysts.


Subject(s)
Carbon Dioxide , Carbonic Anhydrases , Imidazoles , Zinc , Carbonic Anhydrases/metabolism , Carbonic Anhydrases/chemistry , Imidazoles/chemistry , Zinc/chemistry , Carbon Dioxide/chemistry , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/chemical synthesis , Biomimetic Materials/chemistry , Biomimetic Materials/chemical synthesis , Catalysis , Esterases/chemistry , Esterases/metabolism
20.
ACS Appl Bio Mater ; 7(9): 6201-6212, 2024 Sep 16.
Article in English | MEDLINE | ID: mdl-39231419

ABSTRACT

The synthesis of bioinspired metal-organic frameworks (MOFs) performed in mild conditions with a high quality is greatly demanded. Moreover, the influence of the morphology and structure of bio-MOFs on the cell interaction and toxicity is important to determine. In this work, we developed an ultrasound (US)-assisted synthesis of HKUST-1 MOFs under mild conditions and investigated the influence of the parameters of synthesis on the morphology, structure, and biological properties of the developed MOFs. It was found that the US power, reaction time, temperature, and type of solvent composition would affect the morphology, size, and yield of the obtained crystals. Employing the optimal synthetic conditions, five types of HKUST-1 MOFs were prepared, achieving highest yields (67.8-96.2%) and different morphologies (octahedral, dodecahedral, icosahedral). The relationship between the morphological features and biological properties of developed bio-MOFs was evaluated and discussed. The cellular association and cytotoxicity of MOF@US and MOF@US-PARG were studied on various cell cultures, i.e. normal mouse embryonic fibroblasts (MEF NF2), chronic myeloid leukemia (K562), and mouse melanoma (B16-F10). The experimental results showed that MOF@US-PARG has a higher percentage of association compared to MOF@US. It has also been shown that the cytotoxicity depends on the concentration and surface modification of the developed MOFs.


Subject(s)
Biocompatible Materials , Materials Testing , Metal-Organic Frameworks , Particle Size , Mice , Animals , Metal-Organic Frameworks/chemistry , Metal-Organic Frameworks/pharmacology , Metal-Organic Frameworks/chemical synthesis , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Biocompatible Materials/chemical synthesis , Humans , Cell Survival/drug effects , Ultrasonic Waves , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Surface Properties , Cell Proliferation/drug effects , Cell Line, Tumor
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